Process for coloring cellulose textile materials with water-insoluble reactive dyestuffs



United States Patent 3 084,016 PROCESS FOR COLOIENG CELLULOSE TEXTILEMATERIALS WITH WATER-INSOLUBLE REAC- TIVE DYESTUFFS Timothy LeslieDawson, Ian Durham Rattee, Irwin Seltzer, and Arthur Hutchinson Wyld,all of Manchester, England, assignors to Imperial Chemical IndustriesLimited, Millbank, London, England, a corporation of Great Britain NoDrawing. Filed Jan. 25, 1960, Ser. No. 4,190 Claims priority,application Great Britain Feb. 10, 1959 9 Claims. (Ci. s-54.2

This invention relates to a coloring process and more particularly itrelates to a coloring process for cellulose textile materials.

According to the invention there is provided a process for coloringcellulose textile materials which comprises treatingthe cellulosetextile material with one or more water-insoluble reactive dyestuffs, ashereinafter defined, and with an acid-binding agent.

The one or more water-insoluble reactive dyestuffs may be applied to thecellulose textile material by either a dyeing or a printing process.

According to a further feature of the invention there is provided aprocess for dyeing cellulose textile materials which comprises dyeingthe cellulose textile material with an aqueous dispersion of one or morewater-insoluble reactive dyestuifs, as hereinafter defined, inconjunction with a treatment with an acidabinding agent.

The treatment with the acid-binding agent may be carried out prior to,simultaneously with or subsequent to the dyeing of the cellulose textilematerial with the aque ous dispersion of one or more of thewater-insoluble reactive dyestufis.

.As examples of acid-binding agents which may be used in this process ofthe invention there may be mentioned sodium hydroxide, potassiumhydroxide, sodium carbonate, potassium carbonate, sodium metasilioate,trisodium phosphate, tripotassium phosphate, magnesium oxide andammonium hydroxide. If desired substances, for example sodiumtrichloroacetate and sodium bicarbonate, may be used which liberate anacid-binding agent when subjected to the action of heat or steam.

This process of the invention may be conveniently brought about bytreating the cellulose textile material with an aqueous solution orsuspension of the acid-binding agent and then immersing the so-treatedcellulose textile material ina dyebath comprising a dispersion of one ormore water-insoluble reactive dyestulfs, as hereinafter defined, at atemperature of between 0 and 100 C., removing the dyed cellulose textilematerial from the dyebath and if desired subjecting the dyed cellulosetextile material to a treatment in a hot aqueous solution of soap.

If desired the cellulose textile material which has been treated with anaqueous solution or suspension of the acid-binding agent may be passedbetween rollers to remove excess aqueous solution or suspension of theacidbinding agent =and/ or dried before being treated with the aqueousdispersion of the water-insoluble reactive dyestuff.

Alternatively the aqueous dispersion of the water-insoluble reactivedyestutf may be applied by padding to with an aqueous dispersion of oneor more water-insoluble reactive dyestuffs, as hereinafter defined,which also contains an acid-binding agent, passing the so-treated cellu-3,084,016 Patented Apr. 2, 1963 "Fee lose textile material throughrollers, then, if desired drying the cellulose textile material at asuitable temperature, for example C., and then subjecting the cellulosetextile material to the action of heat or steam.

Alternatively the cellulose textile material can be dyed by immersing itin a dyebath comprising an aqueous dispersion of the one or morewater-insoluble reactive dyestuffs which also contains an acid-bindingagent, at a suitable temperature for example between 0 and C., andthereafter removing the cellulose textile material from the dyebath, ifdesired subjecting it to a treatment in a hot aqueous solution of soapand finally drying the dyed cellulose textile material. I

Alternatively this process of the invention may be conveniently broughtabout by applying the aqueous dispersion of the one or morewater-insoluble reactive dyestuffs, as hereinafter defined, to thecellulose textile material by a dyeing or a padding method andsubsequently immersing the colored cellulose textile material in anaqueous solution or suspension of the acid-binding agent, preferably ata temperature between 50 C. and 100 C., or alternatively the coloredcellulose textile material may be padded with an aqueous solution orsuspension of the acid-binding agent, the textile material dried andthen subjected to the action of heat or steam.

Alternatively the cellulose textile material can be dyed by immersing itin a dyebath comprising an aqueous dispersion of the one or morewater-insoluble reactive dyestuffs, preferably at a temperature between20 and 100 C., and after the cellulose textile material has absorbedsome or all of the dyestulf, adding the acid-binding agent andcontinuing dyeing for a period at thesame or a different temperature.

The concentration of the acid-binding agent present in the aqueoussolution or suspension or in the aqueous dispersion of the dyestuffs isnot critical but it is preferred to use between 0.1% and 10% of theacidabinding agent based on the total weight of the aqueous solution orsuspension. If desired the aqueous solution or suspension of the acidbinding agent may also contain further substances, tor exampleelectrolytes such as sodium chloride and sodium sulphate.

The aqueous dispersion of the one or more water-insoluble reactivedyestuffs may also contain substances which are known to assist theapplication of dyestuffs to textile materials, for example sodiumchloride, sodium sulphate, urea, dispersing agents, surface activeagents, sodium alginate or an emulsion of an organic liquid, for exampletrichloroethylene in water.

According to a still further feature of the invention there is provideda process for coloring cellulose textile materials which comprisesprinting the cellulose textile material with a printing paste containingone or more water-insoluble reactive dyestuffs, as hereinafter defined,the printing being carried out in conjunction with a treatment with anacid-binding agent.

The acidabinding agent may be applied to the cellulose textile materialbefore applying the printing paste, or the acidbinding agent may beincorporated into the printing paste, or the printing paste may beapplied to the cellulose textile material and the printed cellulosetextile material subsequently treated with the acid-binding agent.

The cellulose textile material may be printed with the printing paste byany of the commonly known methods of applying printing pastes to textilematerials, for example by means of roller printing, screen printing,block printing, spray printing or stencil printing.

The printing pastes used in this process of the invention may containthe commonly used adjuvants, for example urea, thickening agents, forexample methyl cellulose, starch, locust bean gum, sodium alginate,water-in-oil emulsions, oil-in-water emulsionasurface active agents,

sodium m-nitrobenzene sulphonate, and organic liquids, for exampleethanol.

As examples of acid-binding agents which may be used in this process ofthe invention there may be mentioned sodium hydroxide, potassiumhydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate,sodium metasilicate, magnesium oxide and trisodium phosphate.

This process of the invention may be conveniently brought about byapplying a printing paste containing one or more of the water-insolublereactive dyestuffs, as hereinafter defined, to a cellulose textilematerial which has been impregnated with an acid-binding agent andthereafter subjecting the printed cellulose textile material to theaction of heat or steam.

Alternatively this process of the invention may be conveniently broughtabout by applying a printing paste containing one or more of thewater-insoluble reactive dyestuffs and containing an acid-binding agentto the cellulose textile material and subsequently subjecting theprinted cellulose textile material to the action of heat or steam.

Alternatively this process of the invention may be conveniently broughtabout by applying a printing paste containing one or more of thewater-insoluble reactive dyestuffs to the cellulose textile material andthereafter immersing the printed textile material in a hot aqueoussolution or suspension of the acid-binding agent or alternativelyimpregnating the printed textile material with an aqueous solution orsuspension of the acid-binding agent and subsequently subjecting theprinted textile material to the action of heat or steam.

After applying the printing paste to the cellulose textile material theprinted textile material may, if desired, be dried, for example at atemperature between 20 and 100 C., before subjecting the printed textilematerial to the action of heat or steam.

At the conclusion of dyeing and/or printing processes it is preferred tosubject the so-colored cellulose textile materials to a soapingtreatment, which may be carried out by immersing the colored cellulosetextile materials for a short time, for example 15 minutes, in a hotaqueous solution of soap and/ or detergent, and subsequently rinsing thecolored cellulose textile material in water before drying it.

By the term water-insoluble reactive dyestufi there is meant a disperseor Water-insoluble dyestufi which is free from sulphonic acid andcarboxylic acid groups and which contains (a) at least one reactivehalogen atom or other reactive atom or group, that is to say a halogenatom or other group which is capable of reacting with the cellulosetextile material whereby the dyestulf is attached to the cellulosetextile material by a chemical bond and (b) one or more hydroxy groups.Examples of classes of such water-insoluble reactive dyestutfs includewaterinsoluble dyestuffs containing, besides the one or more hydroxygroups, at least one 1:3 :S-triazinyl radical carrying one or twochlorine or bromine atoms directly attached to the triazine ring, or atleast one pyrimidyl radical carrying one, two or three chlorine orbromine atoms directly attached to the pyrimidine ring, or at least one'y-halogeno-fi-hydroxypropylamino group, or at least onedi-(y-halogeno-fi-hydroxypropyl)amino group, or at least oneB-halogenoalkylsulphamyl group, or at least one ,9- halogenoethoxygroup, or at least one ,B-halogenothioethane group, or at least one'y-halogen-p-hydroxypropylsulphamyl group, or at least onechloracylamino group, or at least one halogenoacyl group, or at leastone sulphonfluoride group, or at least one vinylsulphonylamino group, orat least one halogenoethylsulphonyl group, or at least one thiocyanogroup, or at least one alkylor arylsulphonyloxyalkylsulphonyl group, orat least one alkylor arylsulphonyloxyalkylarninosuphonyl group, or atleast one alkylor arylsulphonyloxyalkylamino group, or at least onealkylor arylsulphonyloxyalkoxy group, or at least one alkylorarylsulphonyoxyalkylaminocarbonyl group, or at least one acryloylaminoor trichloroacryloylamino group, or at least one vinylsulphonyl group,or at least one epoxypropyl group. The water-insoluble dyestuffs ofthese classes may be for example nitro dyestuffs or dyestuffs of theazo, which may be monoazo or polyazo, anthraquinone or phthalocyanineseries which are free from sulphonic and carboxylic acid groups andwhich may contain one or more coordinately bound metal atoms for examplecopper, chromium, nickel and cobalt.

In the above groups halogeno denotes chloro or bromo, alkyl preferablydenotes a lower alkyl radical containing from 1 to 6 carbon atoms, andary preferably denotes a monocyclic aryl radical.

Water-insoluble dyestuffs containing a dichloro 01' dibromo-l :3:S-triazinyl radical may be obtained by reacting one molecularproportion of a water-insoluble dyestufi containing a primary amino orsecondary amino group with one molecular proportion of cyanuric chlorideor cyanuric bromide. Water-insoluble dyestuffs containing a monochloroor monobromo-1:3:5-triazinyl radical may be obtained by reacting onemolecular proportion of a Water-insoluble dyestulf containing a primaryamino or secondary amino group with one molecular proportion of "atriazine of the formula:

wherein X is a chlorine or bromine atom and Y stands for an alkyl, arylor amino group or for an organic radical containing a nitrogen, oxygenor sulphur atom through which it is linked to the triazine ring.

Water-insoluble dyestuffs containing a pyrimidyl radical carrying one ortwo chlorine or bromine atoms directly attached to the pyrimidine ringmay be obtained by interacting substantially cquimolecular proportionsof a water-insoluble dyestuif containing a primary amino or secondaryamino group and a pyrimidine containing at least two chlorine or bromineatoms in the 2, 4, or 6 positions of the pyrimidine ring. As examples ofsuch pyrimidines there may be mentioned 2:4:6-trichloropyrimidine, 2:4:5 fi-tetrachloropyrimidine, 2 4-dibromopyrimidine,2:4-dichloro-6-methylpyrimidine, 2:4-dichlorofi-methoxypyrimidine, 2 46-tribromopyrimidine, 2 :4-dichloro-G-phenylpyrimidine, 2:4-dichloro-6nitropyrirnidine, 2 4-dichloro-S-cyanopyrimidine, 2 :4: G-trichloro-S-cyanopyrimidine, 2:4-dichloro 6 hydroxypyrimidine,2:4:6-trichloro-S-nitropyrimidine and2:4dichloro-5-nitro-6-methylpyrimidine.

Water-insoluble dyestuffs containing at least one 7-halogeno-p-hydroxypropylsulphamyl or B-halogenoalkylsulphamyl group maybe obtained by treating a waterinsoluble dyestufl? containing at leastone sulphonchloride group with a 'y-halogeno-p-hydroxypropylamine or aB- halogenoalkylamine respectively.

Water-insoluble dyestufis containing at least one B- halogenoethoxy orp-halogenothioethane group may be obtained by treating a water-insolubledyestuff containing at least one B-hydroxyethoxy or fl-hydroxythioethanegroup with a halogenating agent.

Water-insoluble dyestuffs containing at least onehalogeno-fi-hydroxypropylamino or diOy-halogeno-fl-hydroxypropyl) aminogroup may be obtained by reacting a water-insoluble dyestufi containingone or more primary amino groups with epichlorohydrin or epibromohydrinand separating the mixture of products so obtained.

Water-insoluble dyestufls containing an epoxypropyl group may beobtained by reacting the corresponding dyestuffs containing a'y-chloro-dhydroxypropyl group with potassium hydroxide.

Water-insoluble dyestuffs containing a vinylsulphone group may beobtained by treating with an alkali, for

example potassium hydroxide, the corresponding dyehydroxyalkoxy orhydroxyalkylaminocar-bonyl group respectivel with an alkylorarylsulphonhalide respectively. Water-insoluble dyestuffs containing atleast one acryloylamino or trichloroacryloylamino group may be obtainedby reacting a water-insoluble dyestulf containing at least one primaryamino group with acryloyl chloride or trichloroacryloyl chloriderespectively.

Water-insoluble dyestutfs containing at least one vinyl- -sulphonylaminogroup may be obtained by reacting a water-insoluble dyestufi containingat least one primary amino group with B-chloroethane sulphonyl chloridewhen the vinylsulphonylamino group is directly obtained.

Water-insoluble azo dyestuffs containing at least one halogenoacyl groupor at least one sulphonfluoride group, or at least onehalogenoethylsulphonyl group may be obtained by coupling a diazotisedamine with a coupling component, the amine and coupling component beingfree from sulphonic acid and carboxyl-ic acid groups and containing atleast one halogenoacyl group, or at least one sulphonfluoride group orat least one halogenoethylsulphonyl group respectively.

In all the above methods for preparing the waterinsoluble dyestuffs usedin the processes of the invention the starting materials are so chosenthat the resulting dyestuffs are free fromsulphonic and carboxylic acidgroups and contain at least one 'hydroxy group.

As specific examples of suitable water-insoluble reactive dyestuffswhich may be used in the process of the invention there may be mentionedZ-hydroxy-S- methyl -4' (4":6 -dichloro 1":3":5" triazin 2"-yla-mino)azobenzene, 2 chloro 4 ethanesulphonyl 4'- N 18 hydroxyethyl N,8 (4:6" dichloro-1":3":5"- triazin-2" ylamino) ethylaminoazobenzene, 2-.hydroxy 5 methyl 4' (4:6" dibromo 1":3":5"- triazin 2" ylamino)azobenzene, 2 hydroxy S-methyl- 4' (4" chloro 6" B hydroxyethylamino1:3:5"- triazin 2" ylamino)azobenzene, 2 hydroxy S-methyl- 4 (4" chloro6" anil-ino 1":3":5 triazin 2"- ylamino)azobenzer1e, 2 hydroxy 5 methyl4' (4"- chloro 6" amino l":3":5" triazin 2" ylamino)- azobenzene, 2chloro 4 ethanesulphonyl 4' N 8- hydroxyethyl N 8 (4" chloro 6" hydroxy-1:3:5"-triazin-2" ylamino) ethylaminoazobenzene, 2- hydroxy 5 methyl 4(4" bromo 6" NzN di- (;3 hydroXyethyDamino 1:3:5 triazin 2"-ylamino)azobenzene, 2 hydroxy 5 methyl 4 (4"- chloro 6" phenyl 1":3":5"triazin 2" ylamino)- azobenzene, 1 4' (4" chloro 6" hydroxy-1":3:5"-triazin 2" ylamino)anilinoanthraquinone, 4' (4"- chloro 6"hydroxytriazin 2" ylamino) 2:4 dinitrodiphenylamine, 3 (4 chloro 6"hydroxyl":3":5" triazin 2" ylamino) 2 nitro 4trifluoromethyldiphenylarnine, 2 hydroxy 5 methyl 4'- (4:6"dichloropyrimidine 2" ylamino)azobenzene, 4 nitro 4 N:N di('y chloro Bhydroxypropyl)- amino azobenzene, 1:4 bis(- chloro ehydroxypropylamino)anthraquinone, 4 ,B-chloroethylsulphamyh phenylazo 4B hydroxyethylaminonaphthalene, 4 chloroethylsulphamyl 2 methyl 5' Nethyl N flhydroxyethylaminoazobenzene, 2 chloro 4 B chloroethylsulphamyl2' methyl 5' di(beta hydroxyethyD- aminoazobenzene, 1 13 hydroxyethyl 4[3 chloroethylamino anthraquinone,- 1:4 (4":65- dichloro- 1":3,":5triazin 2 ylamino)phenylazo 2 naphthol, 1 amino 2 fi bromoethoxy 4hydroxyanthraquinone, 1 amino 4 hydroxy 2 5 (5' chloroethoxy)ethoxy-anthnaquinone and 1- amino-4-hydroxy-2- pflabromoethoxy)ethoxyanthraquinone.

As examples of cellulose textile materials which may be dyed by theprocesses of therinvention there may be mentioned textile materialscomprising natural and regenerated cellulose for example cotton, viscoserayon and linen.

By the processes of the invention there are obtained on cellulosetextile materials level colorations in a wide range of bright shadeswhich have excellent fastness to wet treatments suchas washing, torubbing and to acids, and the colorations so obtained have much betterfast-ness to Wet treatments than the colorations similarly obtained fromthe corresponding dyestuffs which do not contain a hydroxy group orgroups.

The invention is illustrated but not limited by the following examplesin which the parts and percentages are by weight:

Example 1 7 7 Example 2 n I 100 parts of bleached cotton yarn in hankform are treated in an open dye vessel for 1 /2 hours at a temperaturebetween C. and C. in 3000 parts of water containing 1 part of2-hydroxy-5-methyl-4'-[4"-chloro-6- di( ,B-hydroxyethyl) amino-l" 3" 5-triazin-2 ylaminol azobenzene, 150 parts of sodium chloride and 30parts of sodium metasilicate. T he'yarn is then rinsed in water, boiledin weak soap solution, rinsed again in water. and finally dried. i r

The yarn is colored a bright yellow shade which is fast to washing andto light.

Example 3 parts of spun viscose rayon fabric are treated on a dye jigfor 1 /2 hours at a temperature between 80 C. and 90 C. in 1000 parts ofwater containing 1 part of 2- methyl-4-di-(fi-hydroxyethyl)amino-4' Bchloroethylsulphamylazobenzene, 15 parts of sodium chloride and 10 partsof sodium metasilicate. The fabric is then rinsed in water, boiled inweak soap solution, rinsed again in water and finally dried.

The fabric is colored a bright orange shade which is fast to washing andto light.

Example 4 100 parts of a bleached plain weave cotton fabric are paddedwith water containing 1.0% of-sodium metasilicate,

0.2% of a highly sulphonated oil, 1.0% of1:4-biS('ychloro-fl-hydroxypropylamino)anthraquinone and 0. 1 of a fattyalcohol/ethylene oxide condensate and the fabric is then squeezedbetween rollers until its weight is 200 parts. The fabric is then rolledup andaged at a temperaturebetween 80 C. and 90 C. for 2 hours. Thefabric is then rinsed in water, scoured for 15 minutes in a boiling i0.3% aqueous solution of a neutral detergent, rinsed again in water andfinally dried.

The cotton fabric is colored a bright blue shade which is fast towashing.

is printed on cotton fabric by roller printing. The printed cottonfabric is then dried at a temperature of 70 C. and subsequently treatedfor 30 minutes with steam at atmospheric pressure. The printed cottonfabric is then rinsed in water, treated for minutes in an 0.2% aqueoussolution of soap at 100 C., rinsed again in water and finally dried.

A bright reddish-blue print is obtained on the cotton fabric possessingexcellent fastness to Washing and to rubbing.

I The emulsion thickening used in the above example was obtained byadding 80 parts of white spirit to a rapidly stirred mixture of 7 /2parts of an 8% aqueous solution of a modified locust bean gum, 5 partsof a 26.5% aqueous solution of an alkylated phenol/ethylene oxidecondensate and 7 /2 parts of a aqueous solution of a fatty alcohol/ethylene oxide condensate.

Example 6 In place of the printing paste used in Example 5 there is useda printing paste comprising Parts 2-methyl-4-di(fl-hydroxyethyl)amino-4-fl-chloroeth ylsulphamylazobenzene 1 Sodiumm-nitrobenzenesulphonate 1 Sodium bicarbonate 2 Water 61 5% aqueoussodium alginate solution 35 A bright orange print is obtained on thecotton fabric possessing excellent fastness to washing and to rubbing.

Example 7 In place of the printing paste used in Example 5 there is useda printing paste comprising Parts 2hydroxy-5-methyl-4'-[4-chloro-6"-di(fi-hydroxyethyl)amino 1":3":5triazin-2"-ylamino]azobenzene 2 Sodium m-nitrobenzenesulphonate 1 Sodiumbicarbonate 2 Water Emulsion thickening (obtained as described inExample 5) 70 A bright greenish-yellow print is obtained on the cottonfabric possessing excellent fastness to washing and to rubbing.

Example 8 A printing paste comprising Parts 1:4-bis('y-ch1oro [8hydroxypropylamino)anthraquinone 1 Sodium m-nitrobenzenesulphonate 1Water I 28 Emulsion thickening (obtained as described in Example 5)--- I70 is printed on cotton fabric by roller printing. The printed cottonfabric is then dried at a temperature of 70% C. and the dry print paddedthrough an aqueous solution containing 0.5% of sodium hydroxide. Theprinted cotton fabric is then dried at a temperature of 70% C. andtreated for 10 minutes with steam at atmospheric pressure. The printedcotton fabric is then rinsed in water, immersed for 10 minutes in a 0.2%aqueous solution of soap at C., rinsed again in water and finally dried.

A bright blue print is obtained on the cotton fabric possessingexcellent fastness to washing and to rubbing.

Example 9 A printing paste comprising Parts 2hydroxy-5-methyl-4-(4"-6-dichloro-1":3:5"-

triazin-2-ylamino)azobenzene 1 Sodium m-nitrobenzenesulphonate 1 Water28 Emulsion thickening (obtained as described in Example 5)---- 70Example 10 Cotton fabric is impregnated with an 0.5% aqueous solution ofsodium hydroxide, squeezed between rollers,

.until the weight of solution retained by the fabric is equal to theoriginal Weight of the fabric and finally dried. The cotton fabric isthen printed on a roller printing machine with a printing pastecomprising Parts 1:4 bis(7-chloro-fi-hydroxypropylamino) anthraquinone 3Sodium m-nitrobenzenesulphonate 1 Water 26 Emulsion thickening (obtainedas described in Example 5)- 70 and the printed cotton fabric is thendried at a temperature of 70 C. The dried print is then treated for 30minutes with steam at atmospheric pressure, rinsed in water, immersedfor 10 minutes in a 0.2% aqueous solution of soap at 100 C., rinsedagain in water and finally dried.

A bright reddish-blue print is obtained on the cotton fabric possessingexcellent fastness to washing and to rubhing.

Example 11 In place of the printing paste used in Example 5 there 1sused a printing paste comprising Parts 1 5hydroxyethylaminol-('y-chloro-fi-hydroxypropylamino) anthraquinone 1Sodium m-nitrobenzenesulphonate 1 Sodium carbona 2 Water 61 5% aqueoussodium alignate thickening 35 A bright reddish-blue print is obtained onthe cotton fabric possessing excellent fastness to washing and torubbing.

Example 12 In place of the printing paste used in Example there is useda printing paste comprising Parts 1methylamino-4-('y-chloro-p-hydroxypropylamino) anthraquinone Sodiumm-nitrobenzenesulphonate 1 Sodium carbonate 2 Water 26 Emulsionthickeningtobtained as described in Example 5) 70 A bright reddish-blueprint is obtained on the cotton fabric possessing excellent fastness towashing and to rubbing.

Example 13 100 parts of bleached cotton yarn are immersed in a dyebathcomprising 2 parts of 2-hydroxy-5-methyl-4- (4":6"-dichloro 1":3":'5"triazin 2" ylarnino) azobenzene dispersed in 3000' parts of water, whichis held at a temperature of between 18 and 20 C. 90 parts of sodiumchloride are then added, the yarn agitated in the dyebath for 30 minutesand 15 parts of sodium hydroxide are then added. After agitating for afurther hour the cotton yarn is removed from the dyebath, rinsed in coldwater, immersed for 15 minutes in a 0.3% aqueous solution of neutraldetergent at 100 C., rinsed again in water and finally dried.

The cotton yarn is colored a bright yellow shade possessing excellentfastness to washing.

In place of the 90 parts of sodium chloride used in the above examplethere may be used 90 parts of sodium sulphate when a similar result isobtained.

Example 14 100 parts of spun viscose rayon fabric are padded at 1 8 C.in aqueous medium containing 1% of 2-hydroxy- 5methyl-4'-(4:6"-dichloro-1":3:5"-triazin-2"-ylamino) azobenzene, 2% ofsodium bicarbonate, 0.2% of a highly sulphonated oil and 0.1% of a fattyalcohol/ ethylene oxide condensate. The fabric is squeezed betweenrollers until its weight is 200 parts then -it is exposed to steam at100 C. for 5 minutes. The colored fabric is then rinsed in water,immersed for 15 minutes in a 0.2% aqueous solution of soap, rinsed againin water and finally dried.

The viscose rayon fabric is colored a bright yellow shade possessingexcellent fastness to washing.

Example 15 In place of the printing paste used in Example 8 there isused a printing paste comprising Parts 2-hydroxy5-methyl-4'-[4"chloro-6"- dim-hydroxyethyl)amino 1:3:5 triazin 2ylamino]azobenzene 2 Sodium m-nitrobenzenesulphonate 1 Water 27 Emulsionthickening (obtained as described in Example 5) 70 comprises dyeing acellulose'textile material in a dyebath consisting essentially of anaqueous dispersion of a disperse, water-insoluble dyestuft free fromsulfonic acid and carboxylic acid groups and containing a hydroxysubstituent and a group which is capable of reacting with said cellulosetextile material, whereby the dyestuff is attached to the cellulosetextile material by a chemical bond, and which bath also contains anacid-binding agent and subjecting said textile material to the action ofan elevated temperature to complete the reaction of said dyestuff withsaid textile material.

4. Process for coloring a cellulose textile material which comprisespadding a cellulose textile material through an aqueous dispersion of adisperse, water-insoluble dyestuff free from sulfonic acid andcarboxylic acid groups and containing a hydroxy substituent and a groupwhich is capable of reacting with said cellulose textile material,whereby the dyestuff is attached to the cellulose textile material by achemical bond, which dispersion also contains an acid-binding agent, andthereafter subjecting the cellulose textile material to the action of anelevated temperature to complete the reaction of said dyestuff with saidtextile material.

5. Process for coloring cellulose textile materials which comprisestreating the cellulose textile material which has been pre-treated withan aqueous dispersion of a disperse, water-insoluble dyestuff free fromsulfonic acid and carboxylic acid groups and containing a hydroxysubstituent and a group which is capable of reacting with said cellulosetextile material, whereby said dyestuff is attached to the cellulosetextile material by a chemical bond, with an acid-binding agent, andthereafter subjecting the thus-treated cellulose textile material to theaction of an elevated temperature to complete the reaction of saiddyestuff with said textile material.

6. Process for coloring cellulose textile materials which comprisesdyeing the cellulose textile material in a dyebath consistingessentially of an aqueous dispersion of a disperse, water-insolubledyestufl free from sulfonic acid and carboxylic acid groups andcontaining a hydroxy substituent and a group which is capable ofreacting with said cellulose textile material, whereby the dyest-ulf isattached to the cellulose textile material by a chemical bond, and,after at least a portion of said dyestulf in said dispersion has beenabsorbed by said textile material, adding an acid-binding agent andcontinuing dyeing for a further period, and subjecting said textilematerial to the action of an elevated temperature to complete thereaction of said dyestuif with said textile material.

7. Process for coloring cellulose textile materials which comprisesprinting a cellulose textile material, which has been treated with anacid-binding agent, with a printing paste containing a disperse,water-insoluble dyestuff free from sulfonic acid and car-b-oxylic acidgroups and containing a hydroxy substituent and a group which is capableof reacting with said cellulose textile material, whereby the dyestuffis attached to the cellulose textile material by a chemical bond, andthereafter subjecting the cellulose textile material to the action of anelevated temperature to complete the reaction of said dyestuff with saidtextile material.

8. Process for coloring cellulose textile materials which comprisesprinting the cellulose textile material with a printing paste containingan acid-binding agent and a disperse, water-insoluble dyestufi free fromsulfonic acid and carboxylic acid groups and containing a hydroxysubstituent and a group which is capable of reacting with said cellulosetextile material, whereby the dyestuif is attached to the cellulosetextile material by a chemical bond, and thereafter subjecting thecellulose textile material to the action of an elevated temperature tocomplete the reaction of said dyestutf with said textile material.

9. Process for coloring cellulose textile materials which comprisesprinting the cellulose textile material with a printing paste containinga disperse, water-insoluble dyestufif free from sulfonic acid andcarboxylic acid groups and containing a hydroxy substituent and a groupwhich is capable of reacting with said cellulose textile ReferencesCited in the file of this patent UNITED STATES PATENTS 2,741,532 GuthrieApr. 10, 1956 2,895,785 Alsberg et al. July 21, 1959 2,944,871 Atkinsonet al. July 12, 1960 2,978,289 Barker et al. Apr. 4, 1961 2,981,588Haber Apr. 25, 1961 2,995,412 Kleb Aug. 8, 1961 3,009,920 Jaeger et al.Nov. 21, 1961

1. PROCESS FOR COLORING CELLULOSE TEXTILE MATERIAL WHICH COMPRISESTREATING THE CELLULOSE TEXTILE MATERIAL WITH A DISPERSE, WATER-INSOLUBLEDYESTUFF FREE FROM SULFONIC ACID ABD CARBOXYLIC ACID GROUPS ANDCONTAINING A HYDROXY SUBSTITUENT A GROUP WHICH IS CAPABLE OF REACTINGWITH SAID CELLULOSE TEXTILE MATERIAL, WHEREBY THE DYESTUFF IS ATTACHEDTO THE CELLULOSE TEXTILE MATERIAL BY A CHEMICAL BOND, AND WITH ANACID-BINDING AGENT AND SUBJECTING SAID TEXTILE MATERIAL TO THE ACTION OFAN ELEVATED TEMPERATURE TO COMPLETE THE REACTION OF SAID DYESTUFF WITHSAID TEXTILE MATERIAL.